Lubricating oil composition



NOV- 9, 1954 A. DoRlNsoN LUBRIOATING on. COMPOSITION Filed March 21,"1952 .bmw ESN INVENTOR ATTORNEYS y rr o Ln

United States Patent O M 2,694,046 LUBR'ICATI'NG on. CoMPosmoN AmosDorn'son, ParkForest, lill., assi'giior to Sinclair- Refining Company,New York, N. Y., a corporation of Maine My invention relates to achemical additive for oils .and more particularly to an additive whichimparts im proved lubricity and anti-seizureproperties `to lubricatingyoils thereby increasing their usefulness and value as ex` 'tremepressure lubricants and cutting oils.

It is essential that a cutting oil or extreme pressure lubricant provideadequate lubrication under conditions of both high speed and low torqueand low speed and high torque. In order to impart these essentialproperties to lubricating oils, it is conventional to incorporate in thelubricating oils small amounts of an additive, such assulfur-chlorinated fats and oils or sulfur-chlorinated terpene-fatmixtures. I have now found that improved anti-friction and anti-seizureproperties may be imparted 2,694,046 Patented Nov. 9, 1954specifications for No. 2 lard oil call for a maximum of 25 per cent freefatty acid content of the oil, I have thus found that superior lubricantadditives may be prepared by sulfur-chlorinating a mixture ofalpha-pinche and blends of commercial fatty oils 'of enhanced acidity,provided that the blend of commercial oil has a iinal free acidity asoleic acid ofv at least about 3() per cent.

lnthe preparation of a typical additive of my invention, for example, amixture representing 100 parts by weight of alpha-pinene 'and 100 partsbyweight of ccmmercial oleic acid was heated to about 140 F. and 46parts by weight of sulfur monochlo'ride added at a rate such that theheat of reaction maintained the temperature at about 140 to 158 F. Thereaction mixture was kept at about 140 F. for fro'rn about 3 to 4 hoursafter the completion of the addition ofthe sulfur monochloride and wasthen blown with dry air at about 122 F. to purge it of any hydrogenchloride arising from side reactions and decomposition; The miiiture wasnext blown with air at room temperature for` about 2 hours. About 0.2per centy of propylene oxide was added to the reaction mixture tostabilize the product against further evolution of hydrogen chloride. l

Other additives were prepared for test purposes using the aboveprocedure but with various fatty substances replacing the commercialoleic acid. The various fatty substances and blends thereof and thecompositions of the resulting products are indicated in Table I.

TABLE I Additives prepaed by sulfur-chlorination 'of mixtures ofalpha-)ritiene and fatty substances Starting Materials Finished AdditiveAdditive Nn. V S G1 P t P t z z, ercen ercen Terpene Fat par-ts S C1Alpha-Piume, 100 palts't.. Oleie Acid, 1`0 parts 46 9.07 10.2 do i. No.2 Lard Oil, 100 parts 43 9. 00 9. 76 -..d'o .3.: f. No. 2 Lard Qil andOleic 45 9.69 9.10

. ,AeidI 100 parts. v d'o No. 2 Lard Qil and OleieY 45 10. 00 9.03

Aeid,b 100 parts. -.-.-do Methyl Esters of Lard Oil, 100 47 9.47 10.2

parts.

l 7.5% oleic acid and 92.5% No. 2 lard oil; final lfree fatty acidity ofthey blend 27.5%.

b 36.5% oleic acid and 63.5% No. 2 lard oil; nal free fatty acidity ofthe blend 50%.

to lubricating oils Vby incorporating therein a small amount of asulfur-chlorinated mixture of alpha-pinene and oleic acid. I

The product of my inventionl is vprepared by reacting sulfurmonochloride with a mixture of alpha-pinene and oleic acid.Advantageously the mixture of alpha-pinene and oleic acid containsapproximately equal parts of each substance. The improved lubricatingcompositions of my invention comprise lubricating o'ils, either solventor acid treated, having incorporated ltherein about 0:5 to about 4 percent by Weight of the sulfur monoehloridealpha-pinene-oleic acidreaction product.

I have found that sulfur-chlorination of a mixture of alpha-pinene andoleic acid produces an additive unexpectedly superior, when incorporatedin lubricating oils used as extreme pressure lubricants or cutting oils,to an additive obtained by sulfur-chlorinating a mixture of alpha-pincheand a neutral fat such as methyl esters of lard oil or prime lard oil.For example, I have found that at concentrations f the order of 0.5 percent by weight of my novel additive in a heavy lubricating base oil,improved lubricity at moderate loads and superior anti-seizureproperties at higher loads are realized. .ln addition, this superiorbehavior is associated with similar wear at moderate loadings andprobably with not more than 5 per cent excess Wear at higher loadings ofthat induced by sulfur chloride-pinene-neutral fat reaction productadditives.

I have also found that sulfur-chlorinating a mixture of alpha-pinene anda blend of No. 2 lard oil and oleic acid yields an additive which issuperior, when used in lubricants, to one prepared bysulfur-chlorinating a mixture of alpha-pinche and No. 2 lard oil. Sincecommercial Arun for a full minute at eaclrload level;

The commercial oleic acid used in the preparation of additives I, lliand IV was a low titer, distilled red oil having an iodine value of93.7. The No. 2 lard oil used in preparing additives Ii, ill, and IV hada free fatty acidity as oleic acid of 21.5 per cent and an iodine 'valueof 68.7. The free fatty acidity as oleic acid of the methyl esters oflard oil used in preparing additive V was 2.4 per cent and its iodinevalue was 78.9.

Evaluation of these additives was made on a Falex testing machine by themethod designated as the regular or standard Falex test. in this methodthe load is applied in 259 pound increments and the machine is allowedto Although additives may be evaluated on a Falex testing machinel bythe cutting oil breakdown method in which the load is increasedcontinu'ousl'y at a constant rate, a more severe test than the regularFalex n1e, thodduplicate runs 4tend Since it is desirable to use thetesting method with the fewest sporadic errors, tbe results describedbelow are those obtained by the regular lalex procedure, the differencesamong the various additives being accentuated by reducing theirconcentrations in the oil blends.

In evaluating additives with the Falex machine it is generally acceptedthat the lubricity of an additive, as characterized by the slope of thecurve at moderate loadings, is a different phenomenon than itsanti-seizure properties, characterized by plateau-like regions in thecurve. Figure l presents in graphical form the Falex data for 1/2 percent solutions of additives I, Il, and V, respectively, in a heavylubricating base oil as well as data for additive I at 1A per cent.Gross visual inspec- `tion is sulicient to perceive the superiority of1/2 addi- 3 tive I over 1/2% additive V. Also, 1,4% additive I showssubstantially the same superiority over 1/2% additive V up to a load of2500 lbs., when a sudden transition, indicating the onset of incipientseizure, shifts the curve to a new torque plateau at about the samelevel as the plateau for 16% additive V. The curve for l/2% additive IIstarts oi better than the curve for 1/2% additive V (compare regions iand ii in the rst-named curve with the sharp rise of region i in thesecond), but the sudden transitional rise to a torque of 55 lbs/ft. at1250 lbs. load is suilicient to put 1/z% additive 1I in the samebehavior class with 1/2 additive V at loads higher than 1000 lbs.Further, only gross visual inspection of the graph is required todemonstrate the superiority of 1/27/2 additive I over 1/2 additive II atloads greater than 1000 lbs. Table II summarizes the salient features ofFigure l.

TABLE II Falex testing of additives ADDITIVE I (36%) Torque` Load RangeAverage Average Description lbs. Rane, lbs. Torque Slope Plateau A 1,500-2, 250 28-30 0. 0027 ADDITIVE I (54%) Plateau 0.... 1,7502,500 0.00435 Plateau D. 3, 500-4, 000 0 Transitian (a) 2, 5002,750 0.108Transition (b) 2, 750-3, 500 0. 017 Region i 0-250 0. 048 Region ii250-750 0. 016 Region lli 750-1, 750 0. 010

ADDITIVE 1I Plateau 2, 500-4, 000 47-50 48 0. 0020 Transition (a) l,000-1, 250 25-55 0.120

1,250-1, 75o -o. oso 45 ADDITIVE III Plateau 1,750-2,750 B7-39 38 0.0020 Transition. l, 250-1 750 0. 024 Region i. 0-250 0.044 Region il250-1, 250 0. 014

ADDITIVE IV (15%) 0-250 0.048 60 Region 1i.. Z50-1, 250 0.018

ADDITIVE V Plateau 1,500-4, ooo sii-52 5o o 65 Transition 1, 250-1, 50052-50 *0. 008 Regioni 0-1, 250 0-56 0. 045

sures and were subjected to the two hour test on the fourball machine todetermine their wear characteristics atl TABLE III Timken testing ofadditives 2% ADDITIVE I Pressure Scar Width, mm. LVIS kgmJsq.

TABLE IV F our-ball resting of additives Pressure Load, kgm Wear, cc.kgil-sq. Ratio Base Oil b 7 0. 0868 1, 400 1:1. 00 2%Additive I- 70.0904 1,100 1:1.04 2% Additive V 7 0. 0868 1, 400 1:1.00 Base O115..... 20 0.1008 22,000 1:1.00 2% Additive I 20 0.1008 22, 000 1:1. 002% Additive V. 20 0.1008 22,000 1:1.00 Base Oil b--.. Y 35 0.1044 36,1001:1.00 2% Additive I. 35 0.1198 24, 400 1:1.15 2% Additive V 35 0.104436,100 1:1.00 Base Oil b... 60 0.1206 46,500 1:1.00 2% Additive 600.1434 30,000 1:1. 19 2% Additive V. 60 0.1204 40,100 1:1. 00

Wear with additive divided by Wear with 1005 oil. b Solvent-renedMid-Continent, oil of S. U. S. at 100 F.

I claim: i l. As a composition of matter useful for the purpose ofimparting lubricity and anti-seizure properties to lubricating oils, theproduct formed by the reaction of about 45 parts of sulfur monochlorideand a mixture compris- References Cited in the le of this patent UNITEDSTATES PATENTS Number Name Date 2,422,275 Winning et al June 17, 19472,606,182 Musselman Aug. 5, 1952

2. A LUBRICATING OIL COMPOSITION WHICH COMPRISES A MINERAL LUBRICATINGOIL HAVING INCORPORATED THEREIN ABOUT 0.5 TO ABOUT 4 WEIGHT PER CENT OFTHE PRODUCT FORMED BY THE REACTION OF ABOUT 45 PARTS OF SULFURMONOCHLORIDE AND A MIXTURE COMPRISING ABOUT 100 PARTS OF ALPHA-PINENEAND ABOUT 100 PARTS OF OLEIC ACID AT A TEMPERATURE OF ABOUT 140* TO 158*F.